AU8954398A - Polycarbonate redistribution method with catalyst decomposition - Google Patents
Polycarbonate redistribution method with catalyst decomposition Download PDFInfo
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- AU8954398A AU8954398A AU89543/98A AU8954398A AU8954398A AU 8954398 A AU8954398 A AU 8954398A AU 89543/98 A AU89543/98 A AU 89543/98A AU 8954398 A AU8954398 A AU 8954398A AU 8954398 A AU8954398 A AU 8954398A
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- polycarbonate
- composition
- compound
- polyhydroxyaliphatic
- hydroxide
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- 229920000515 polycarbonate Polymers 0.000 title claims description 54
- 239000004417 polycarbonate Substances 0.000 title claims description 54
- 238000000034 method Methods 0.000 title claims description 35
- 239000003054 catalyst Substances 0.000 title claims description 24
- 238000000354 decomposition reaction Methods 0.000 title description 9
- 239000000203 mixture Substances 0.000 claims description 53
- 150000001875 compounds Chemical class 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 229940075507 glyceryl monostearate Drugs 0.000 claims description 5
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical class C* 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical group CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 claims 3
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 claims 2
- -1 diaryl carbonate Chemical compound 0.000 description 14
- 229920005862 polyol Polymers 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 150000003077 polyols Chemical class 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000006085 branching agent Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 150000004679 hydroxides Chemical class 0.000 description 4
- DJFBJKSMACBYBD-UHFFFAOYSA-N phosphane;hydrate Chemical compound O.P DJFBJKSMACBYBD-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000007824 aliphatic compounds Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- 239000005968 1-Decanol Substances 0.000 description 1
- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 description 1
- RZRNAYUHWVFMIP-GDCKJWNLSA-N 3-oleoyl-sn-glycerol Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@H](O)CO RZRNAYUHWVFMIP-GDCKJWNLSA-N 0.000 description 1
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 1
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/42—Chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Catalysts (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Our Ref: 689577 P/00/011 Regulation 3:2
AUSTRALIA
Patents Act 1990
ORIGINAL
COMPLETE
SPECIFICATION
STANDARD PATENT Applicant(s): t t General Electric Company One River Road Schenectady New York 12345 UNITED STATES OF AMERICA DAVIES COLLISON
CAVE
Patent Trade Mark Attorneys Level 10, 10 Barrack Street SYDNEY NSW 2000 Address for Service: Polycarbonate redistribution method with catalyst decomposition Invention Title: The following statement is a full description of this invention, including the best method of performing it known to me:- 5020
I~
RD-25606 -1- POLYCARBONATE REDISTRIBUTION METHOD WITH CATALYST
DECOMPOSITION
BACKGROUND OF THE INVENTION This invention relates to the redistribution of polycarbonates, and more particularly to a redistribution method employing a tetraorganophosphonium hydroxide as catalyst and an agent for decomposition of said catalyst.
Polycarbonates have traditionally been prepared by an I 10 interfacial method involving the reaction of a dihydroxyaromatic compound with phosgene, or a melt method in which the phosgene is replaced by a diaryl carbonate. In recent years, however, a redistribution process for use with polycarbonates has been developed. This process, described in US Patents 5,414,057 and 5,459,226, comprises heating an already formed polycarbonate in the presence of a redistribution catalyst to produce a polycarbonate with a different, generally lower, molecular weight. The method is highly Kuseful commercially because it permits the preparation from monomeric materials of a single high molecular weight polycarbonate, which may then undergo redistribution to yield a spectrum of lower molecular weight materials which can be custom designed depending on their intended uses. A similar method, applicable to polyestercarbonates, is disclosed in US Patent 5,652,312.
A broad spectrum of redistribution catalysts is disclosed in 5,414,057, and the use of tetraorganophosphonium carboxylates as catalysts is disclosed in 5,459,226. Another excellent class of catalysts, disclosed in US Patent 5,567,802, is the tetraorganophosphonium hydroxides. They are frequently characterized by high efficiency. However, according to the procedure described in that patent the tetraorganophosphonium hydroxide RD-25606 -2remains in the polycarbonate after redistribution and can cause hydrolytic, melt and color instability.
SThere is a.need, therefore, for materials which can be incorporated into redistribution mixtures containing tetraorganophosphonium hydroxides as catalysts and which cause decomposition of the catalyst after its function has been performed.
Thus, such materials would have two requirements: to function only after redistribution has taken place and to cause efiicient decomposition of the catalyst to harmless materials.
SUMMARY OF THE INVENTION The present invention provides a method and compositions for polycarbonate redistribution which have the above-listed advantages. It is based on the discovery that aliphatic polyols are effective reagents for decomposition of tetraorganophosphonium hydroxides after completion of their function as redistribution catalysts.
In one of its aspects, therefore, the invention is a method for redistributing an organic polycarbonate composition which comprises contacting, at a temperature effective for redistribution, an initial organic polycarbonate composition characterized by an initial l weight average molecular weight, with a redistributing amount of at least one tetraorganophosphonium hydroxide as catalyst and a catalyst decomposing amount of at least one polyhydroxyaliphatic compound, thereby forming a polycarbonate composition having a weight average molecular weight different from said initial molecular weight.
SAnother aspect-of the invention is polycarbonate compositions capable of redistribution, said compositions comprising an organic polycarbonate composition, tetraorganophosphonium hydroxide and polyhydroxyaliphatic compound as described ~hereinabove.
RD-25606 -3- DETAILED DESCRIPTION; PREFERRED EMBODIMENTS Any linear or branched polycarbonate composition is an acceptable starting material for the method of this invention. Suitable polycarbonate compositions include aromatic and aliphatic polycarbonates.
Preferably, the initial polycarbonate composition is an aromatic polycarbonate. Such polycarbonates typically consist essentially of structural units of the formula 0
II
O--R-0-C I 10 wherein at least about 60 percent of the total number of R groups are aromatic organic radicals and the balance thereof are ,ilatic, I 'alicyclic, or aromatic radicals. More preferably, R is an aromatic organic radical and still more preferably a radical of the formula (II) A' Y-A 2 15 wherein each A' and A 2 is a monocyclic divalent aryl radical and Y is a bridging radical in which one or two carbon atoms separate A and A 2 Such radicals frequently are derived from dihydroxyaromatic compounds of the formula HO-A' Y--A 2
OH
For example, A' and A 2 typically represent unsubstituted phenylene or substituted derivatives thereof. The bridging radical Y is most often a H hydrocarbon group and particularly a saturated group such as methylene, cyclohexylidene or isopropylidene. The most preferred dihydroxyaromatic compound is bisphenol A, in which each of A' and
A
2 is p-phenylene and Y is isopropylidene.
I Typically, the weight average molecular weight of the initial polycarbonate composition may range from values as low as 500 i-, RD-25606 -4to values as high as 200,000, as measured by gel permeation chromatography relative to polystyrene. Preferably, the weight average molecular weight of the initial polycarbonate composition ranges from about 5,000 to about 100,000; more-preferably, from about 25,000 to about 65,000.
Copolymers, as well as homopolymers, can be redistributed according to the method of the invention. Two or more different dihydroxyaromatic compounds may be employed in the preparation of the copolymer. Alternatively, a copolymer prepared from a mixture of a dihydioxyaromatic compound with a glycol, such as ~propylene glycol, or with a hydroxy- or acid-terminated polyester may be redistributed. Copolyestercarbonates, prepared from the reaction of a dihydroxyaromatic compound with the combination of a carbonate source and a dibasic acid such as adipic acid, suberic acid, azelaic acid, 1,1 2 -dodecanedicarboxylic acid or terephthalic acid, may also be S redistributed. Further, blends of aromatic polycarbonate homopolymer .with any of the above-described copolymers may be employed.
Branched polycarbonates may also be used as the initial composition. Any of the commercially available branched aromatic 20 polycarbonates may be used, such as those disclosed in US Patents o 3,541,049, 3,799,953, 4,185,009, 4,469,861 and 4,431,793, all of :which are incorporated by reference herein in their entirety.
The method of the invention involves melt equilibrating the initial polycarbonate composition in the presence of two materials.
The first material is a tetraorganophosphonium hydroxide, preferably a tetraalkyl- and most preferably a tetra-(C 1 alkyl)phosphonium hydroxide. Tetra-n-butylphosphonium hydroxide is often preferred.
S The second material is at least one polyhydroxyaliphatic compound, hereinafter sometimes designated "polyol". In general, any aliphatic compound containing at least two free hydroxy groups may be employed. The preferred polyols are compounds containing about 2-6 carbon atoms and ether and ester derivatives thereof, provided at 1 1 RD-25606 least two free hydroxy groups per molecule are present. Illustrative compounds of this type are ethylene glycol, propylene glycol, neopentylene glycol, pentaerythritol, glycerol, and various acylated derivatives of these compounds, such as glyceryl monostearate and glyceryl monooleate.
It has been found that monohydroxy compounds, including aliphatic and aromatic compounds, decompose tetraorganophosphonium hydroxides to some extent under the conditions employed according to the invention. However, their effectiveness at a given concentration is much lower than that of the aliphatic polyols. Thus, the use of monohydroxy compounds is not contemplated as part of the present invention.
Typically, when the starting material is a single homopolymer or copolymer, redistribution converts the starting polycarbonate into a redistributed polycarbonate having a weight average molecular weight which is lower than the starting weight.
S" When the starting composition is a blend of homopolymers or copolymers of different molecular weights, it is possible for the redistributed composition to have a molecular weight higher than at least one starting component and lower than at least one other starting component.
:opai' Preferably, the method of this invention does not include incorporation into the starting materials of branching agents.
Examples of such branching agents are trimellitic anhydride acid chloride, cyanuric chloride and phenolic compounds having two or more hydroxy groups per molecule, for example 1,1,1 -tris(4-hydroxyphenyl)ethane. Branching agents of this type will be recognized b those skilled in the art of polycarbonate synthesis and are described in U.S. Patents 5,021,521 and 5,097,008. Such branching agents are known to equilibrate with linear aromatic polycarbonate compositions to form branched aromatic polycarbonate compositions..- 4 t RD-25606 -6- The amount of tetraorganophosphonium hydroxide employed as redistribution catalyst may be any amount which is effective in promoting the redistribution process. Usually the effective amount will depend upon such parameters as the reaction rate desired, the molecular weight desired in the redistributed composition, and to a lesser extent the chemical nature of the initial polycarbonate composition. Depending upon such variables, an effective amount of catalyst can easily be determined without undue experimentation. The preferred amount is generally in the range of about 15-1,000 moles per million moles of carbonate structural units in the initial polycarbonate composition.
The amount of polyol is an amount effective to decompose the catalyst after its action is complete. In general, this amount will be in the range of about 250-750 ppm by weight based on 15 initial polycarbonate composition, with about 250-600 ppm often being preferred.
It is generally preferred that at least a small proportion of water be present in the redistribution mixture to promote the reaction.
This may be achieved by employing an aqueous solution of the 20 tetraorganophosphonium hydroxide, typically a 20-60% solution by weight.
SOptionally, a diaryl carbonate may be added to the initial S* polycarbonate composition. The diaryl carbonate functions to control molecular weight and serves as an efficient endcapping agent. Diaryl carbonates which are suitable include diphenyl carbonate and Ssubstituted diphenyl carbonates provided that the substituent is inert I with respect to the redistribution process. Typical inert substituents include alkyi, halo, cyano, alkoxy, carboxy, aryl and nitro moieties.
Preferably, the diaryl carbonate is unsubstituted diphenyl carbonate.
The amount of diaryl carbonate may be any amount which provides the desired molecular weight in the redistributed Spolycarbonate composition. Usually, the amount of diaryl carbonate is
I
*P RD-25606 -7no greater than about 1.5 weight percent based upon the amount of starting polycarbonate, more preferably, no greater than about weight percent.
The method of this invention can be effected by dry mixing the starting organic polycarbonate, the carbonate redistribution catalyst, the polyol and, optionally, the diaryl carbonate, and melt equilibrating the resulting mixture at a temperature effective for redistribution, typically in the range of about 180-320 °C and preferably about 250-3000C. Typical melt processing techniques are melt condensation in a Helicone reactor for approximately 5-30 minutes, and continuous extrusion through a single screw or twin screw extrusion device. One skilled in the art will recognize that if extrusion is employed, the screw speed and feed rate may vary. During heating, it may be necessary to vent gases formed during decomposition of the catalyst.
It is an advantage of the method of this invention that the molecular weight of the redistributed polycarbonate composition may be controlled to a fine degree. Control is generally obtained simply by varying the amounts of redistribution catalyst and diaryl carbonate employed in the redistribution process. In such a manner, it is possible to obtain from a single polycarbonate composition a variety of lower molecular weight redistributed compositions heretofore available only by interfacial or melt polymerization methods.
It is also possible to redistribute a mixture of high and lower molecular weight polycarbonates to obtain a polycarbonate of intermediate molecular weight. The latter generally have narrower Smolecular weight distributions, as represented by dispersivity (Mw/Mn), and lower melt viscosities than simple blends of the high and low molecular weight resins. Mixtures of linear and branched resins may i 30 also be redistributed. Finally, recycled polycarbonates, as illustrated Sby the linear optical disk grades and the branched blow molding grades, may be redistributed individually or in admixture; the products 1 RD-25606 -8have the high ductility of the non-redistributed simple blends as well as other desirable properties.
The invention is illustrated by a series of examples in which a bisphenol A homopolycarbonate having a weight average molecular weight, as determined by gel permeation chromatography relative to polystyrene, of 34,000 was extruded on a twin screw extruder at 260°C with 125 ppm by weight, based on polycarbonate, or tetra-n-butylphosphonium hydroxide and various amounts of polyols ("GMS" designating glyceryl monostearate). The extrudates were analyzed for residual tetra-n-butylphosphonium hydroxide .ind their molecular weights were determined. The results are given in the following table. Comparison was made with various controls empoying no phosphonium hydroxide, no polyol and various monohydroxy compounds as replacements for polyol.
I-
-I
I s RD-25606 Hydroxy compound Fvn mnIl Residual Product phosphonium Wt., Dpm Mw cpd, ppm Identity Pyam leT' Identity 22.5 Ii 1 2 3 4 6 7 Control 1* Control 2 Control 3 Control 4 Control 5.
Control 6 Control 7 Control 8 Control 9 Control 10 Control 11
GMS
GMS
GMS
GMS
GMS
Pentaerythritol Ethylene glycol Phenol 1-Decanol u t-Butanol u 100 200 300 400 500 300 300 300 300 600 900 1,200 300 600 900 1,200 32,200 32,200 31,400 31,300 29,200 29,200 22.5 16.5 2.2 2.1 0 0 29.700 34,000 32,300 31,100 33,300 28,400 28,900 28,900 31,500 30,000 29,100 29,600 28.5 22.5 16.0 17.4 20,3 20.0 16.0 16.8 *No phosphonium hydroxide It is apparent from the table that glyceryl monostearate, pentaerythritol and ethylene glycol at levels of 300 ppm afforded products with very little or no detectable phosphonium hydroxide. By contrast, the controls employing monohydroxy compounds at the same level afforded products having substantially higher proportions of phosphonium hydroxide. Only Controls 6 and 7, employing 1-decanol at substantially higher levels, approached the polyols in effectiveness of catalyst decomposition
I-
P.\WPDOCSVPATCOMPMRSE-23llWi 9a Throughout this specification and the claims which follow, imless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps.
i. 2.:
Claims (8)
- 2. A method according to claim 1 wherein the temperature is in the range of about 180-320 oC. s
- 3. A method according to claim 2 wherein the polycarbonate is a bisphenol A polycarbonate. I 4. A method according to claim 2 wherein the tetraorganophosphonium hydroxide is a tetraalkylphosphonium hydroxide. S 5. A method-according to claim 4 wherein the tetraalkylphosphonium hydroxide is tetra-n-butylphosphonium hydroxide.
- 6. A method according to claim 2 wherein the polyhydroxyaliphatic compound is a compound containing about 2-6 Hj carbon atoms or an ether or ester derivative thereof.
- 7. A method according to claim 6 wherein the polyhydroxyaliphatic compound is glyceryl monostearate.
- 8. A method according to claim 6 wherein the polyhydroxyaliphatic compound is pentaerythritol. RD-25606 -11-
- 9. A method according to claim 6 wherein the polyhydroxyaliphatic compound is ethylene glycol. A method according to claim 2 wherein the proportion oftetraorganophosphonium hydioxide is in the range of about 50-1000 moles per million moles of carbonate structural units in the initial polycarbonate composition.
- 11. A method according to claim 2 wherein the proportion of polyhydroxyaliphatic compound is in the range of about
- 250-750 ppm by weight based on initial polycarbonate composition. 12. A polycarbonate composition capable of redistribution, said composition comprising an initial organic: polycarbonate composition characterized by an initial weight average molecular weight, a redistributing amount of at least one tetraorganophosphonium hydroxide as catalyst and a catalyst decomposing amount of at least one polyhydroxyaliphatic compound. 13. A composition according to claim 12 wherein the polycarbonate is a bisphenol A polycarbonate. 14. A composition according to claim 12 wherein the tetraorganophosphonium hydroxide is a tetraalkylphosphonium hydroxide. A composition according to claim 12 wherein the polyhydroxyaliphatic compound is a compound containing about 2-6 carbon atoms or an ether or ester derivative thereof. 16. A composition according to claim 15 wherein the polyhydroxyaliphatic compound is glyceryl monostearate. 17. A composition according to claim 15 wherein the Ipolyhydroxyaliphatic compound is pentaerythritol. ~ii, -2310/98 -12- 18. A composition according to claim 15 wherein the polyhydroxyaliphatic compound is ethylene glycol. 19. A composition according to claim 12 wherein the proportion of tetraorganophosphonium hyroxide is in the range of about 50-1000 moles per million moles of carbonate structural units in the initial polycarbonate composition. A composition according to claim 12 wherein the proportion of polyhydroxyaliphatic compound is in the range of about 250-750 ppm by weight based on initial polycarbonate 10 composition. 21. Methods and composition for polycarbonate redistribution, substantially as hereinbefore described with reference to the Examples. 15 DATED this 23rd day October 1998 4 GENERAL ELECTRIC COMPANY By its Patent Attorneys DAVIES COLLISON CAVE .e I
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/963,177 US5886073A (en) | 1997-11-03 | 1997-11-03 | Polycarbonate redistribution method with catalyst decomposition |
| US08/963117 | 1997-11-03 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU8954398A true AU8954398A (en) | 1999-05-20 |
| AU744749B2 AU744749B2 (en) | 2002-02-28 |
Family
ID=25506852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU89543/98A Ceased AU744749B2 (en) | 1997-11-03 | 1998-10-26 | Polycarbonate redistribution method with catalyst decomposition |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5886073A (en) |
| EP (1) | EP0913419B1 (en) |
| JP (1) | JPH11199666A (en) |
| KR (1) | KR19990044950A (en) |
| CN (1) | CN1220286A (en) |
| AU (1) | AU744749B2 (en) |
| BR (1) | BR9804386A (en) |
| DE (1) | DE69822959T2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6436503B1 (en) | 1999-09-08 | 2002-08-20 | General Electric Company | Data storage medium containing polyestercarbonate |
| KR100767888B1 (en) * | 2000-04-11 | 2007-10-17 | 제너럴 일렉트릭 캄파니 | Process for redistribution of polycarbonate |
| US6492485B1 (en) | 2000-04-11 | 2002-12-10 | General Electric Company | Redistributed polycarbonate resin |
| US7321014B2 (en) * | 2004-12-29 | 2008-01-22 | General Electric Company | Transparent compositions, methods for the preparation thereof, and articles derived therefrom |
| US7326764B2 (en) | 2005-05-20 | 2008-02-05 | General Electric Company | Transparent compositions, methods for the preparation thereof, and articles derived therefrom |
| US7273917B2 (en) * | 2005-05-20 | 2007-09-25 | General Electric Company | Transparent compositions, methods for the preparation thereof, and articles derived therefrom |
| US7323536B2 (en) | 2005-05-20 | 2008-01-29 | General Electric Company | Transparent compositions, methods for the preparation thereof, and articles derived therefrom |
| US7323535B2 (en) * | 2005-05-20 | 2008-01-29 | General Electric Company | Transparent compositions, methods for the preparation thereof, and articles derived therefrom |
| US8343608B2 (en) | 2010-08-31 | 2013-01-01 | General Electric Company | Use of appended dyes in optical data storage media |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3541049A (en) * | 1969-08-21 | 1970-11-17 | Mobay Chemical Corp | Cyanuric chloride branched polycarbonates |
| US3799953A (en) * | 1972-09-01 | 1974-03-26 | Bayer Ag | 1,4-bis(4,'4''-dihydroxy-triphenylmethyl)benzene |
| US4185009A (en) * | 1975-01-03 | 1980-01-22 | Bayer Aktiengesellschaft | Branched, high-molecular weight thermoplastic polycarbonates |
| US4431793A (en) * | 1982-06-09 | 1984-02-14 | General Electric Company | Aromatic polycarbonate end capped with branched chain alkyl acyl halide or acid |
| US4469861A (en) * | 1982-12-27 | 1984-09-04 | General Electric Company | Polycarbonate composition from branched chain dihydric phenol |
| EP0272417A3 (en) * | 1986-12-22 | 1989-09-27 | General Electric Company | Blends of polycarbonate resins and polyester resins exhibiting improved color properties |
| JPH0826140B2 (en) * | 1987-06-24 | 1996-03-13 | 大日本インキ化学工業株式会社 | Method for producing polycarbonate carbonate |
| US5021521A (en) * | 1989-01-17 | 1991-06-04 | General Electric Company | Process of reacting branched thermoplastic polycarbonate with polyhydric phenol having more than two hydroxy groups |
| US5097008A (en) * | 1989-06-01 | 1992-03-17 | General Electric Company | Preparation of branched polycarbonate from oligomeric cyclic polycarbonate and polyhydric phenol |
| DE4036359A1 (en) * | 1990-11-15 | 1992-05-21 | Hoechst Ag | METHOD FOR PREVENTING THE PROCESSING OF A PLASTIC MOLD AT THE PROCESSING TEMPERATURE |
| JP2674636B2 (en) * | 1991-12-19 | 1997-11-12 | 信越化学工業株式会社 | Organopolysiloxane rubber composition |
| EP0595608B1 (en) * | 1992-10-30 | 1997-07-16 | General Electric Company | Redistribution of organic polycarbonate compositions |
| US5459226A (en) * | 1994-07-27 | 1995-10-17 | General Electric Company | Polycarbonate redistribution method |
| US5652312A (en) * | 1995-01-17 | 1997-07-29 | General Electric Company | Redistribution of organic polyestercarbonate compositions |
| US5605979A (en) * | 1995-05-22 | 1997-02-25 | Bayer Corporation | Method for modifying the backbone of polymeric resins |
| US5567802A (en) * | 1995-11-20 | 1996-10-22 | General Electric Company | Polycarbonate redistribution method employing phosphonium hydroxides |
| US5863992A (en) * | 1996-07-15 | 1999-01-26 | General Electric Company | Tetraphenols and their use as polycarbonate branching agents |
-
1997
- 1997-11-03 US US08/963,177 patent/US5886073A/en not_active Expired - Lifetime
-
1998
- 1998-10-23 EP EP98308710A patent/EP0913419B1/en not_active Expired - Lifetime
- 1998-10-23 DE DE69822959T patent/DE69822959T2/en not_active Expired - Lifetime
- 1998-10-26 AU AU89543/98A patent/AU744749B2/en not_active Ceased
- 1998-11-02 KR KR1019980046844A patent/KR19990044950A/en not_active Application Discontinuation
- 1998-11-02 JP JP10311622A patent/JPH11199666A/en not_active Ceased
- 1998-11-03 BR BR9804386-2A patent/BR9804386A/en not_active Application Discontinuation
- 1998-11-03 CN CN98123737A patent/CN1220286A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN1220286A (en) | 1999-06-23 |
| EP0913419B1 (en) | 2004-04-07 |
| US5886073A (en) | 1999-03-23 |
| DE69822959D1 (en) | 2004-05-13 |
| EP0913419A3 (en) | 2000-05-10 |
| DE69822959T2 (en) | 2005-03-24 |
| JPH11199666A (en) | 1999-07-27 |
| EP0913419A2 (en) | 1999-05-06 |
| BR9804386A (en) | 2001-02-20 |
| KR19990044950A (en) | 1999-06-25 |
| AU744749B2 (en) | 2002-02-28 |
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